CN106336476A - Preparation method of vinylidene fluoride copolymer having high breaking elongation - Google Patents
Preparation method of vinylidene fluoride copolymer having high breaking elongation Download PDFInfo
- Publication number
- CN106336476A CN106336476A CN201610722760.2A CN201610722760A CN106336476A CN 106336476 A CN106336476 A CN 106336476A CN 201610722760 A CN201610722760 A CN 201610722760A CN 106336476 A CN106336476 A CN 106336476A
- Authority
- CN
- China
- Prior art keywords
- vinylidene
- preparation
- consumption
- quality
- vinylidene fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of a vinylidene fluoride copolymer having high breaking elongation, and belongs to the technical field of polymer material fluorine elastomers. The preparation method comprises: 1) purging nitrogen to remove oxygen in a sealed polymerization reaction kettle, and adding deionized water, an initiator, a dispersant, a chain transfer agent, a second monomer, and a vinylidene fluoride monomer; 2) increasing the temperature of the reaction kettle to 30-70 DEG C, and carrying out a reaction for 4-8 h under a reaction pressure of 9.0-12.0 Mpa at a rotation speed of 1000-2000 rotation/min to prepare a vinylidene fluoride polymer slurry; and 3) carrying out high temperature stirring degassing on the polymer slurry, washing the slurry by using deionized water, and carrying out flash evaporation drying on the collected slurry to prepare the finished product. According to the present invention, with the preparation method, the prepared polymer has characteristics of high breaking elongation, low melting point, low crystallization temperature, good impact strength, and the like.
Description
Technical field
The invention belongs to macromolecular material fluororesin synthesis technical field, the inclined fluorine second of specially a kind of high elongation at tear
The preparation method of alkene copolymer.
Background technology
Polyvinylidene fluoride resin has excellent mechanical property, solvent resistant, heat resistance, good weatherability and anti-oxidant spy
Property, it is widely used in the fields such as chemical industry, lithium battery binding agent, photovoltaic back film, membrane for water treatment, coating.But Kynoar
Because degree of crystallinity is high, strand compliance not, leads to it often product in electric wire process easy to crack, extrusion
Pressure is high, the problems such as pliability difference.For solving this difficult problem, researcher develops vinylidene fluoride copolymers.
Vinylidene fluoride copolymers refer to the polymer of vinylidene and second comonomer copolymerization, are drawn by second comonomer
Enter, change molecular chain structure, impart the new characteristic of polymer, such as: high elongation at tear, high-adhesion, high fluidity
Deng.High elongation at tear vinylidene fluoride copolymers are low due to fusing point, and crystallization temperature is low, and impact strength is good, is widely used in
Electric wire manufacture field.
At present, domestic and international researcher has done a lot of work to the development of high elongation at tear vinylidene fluoride copolymers, relates to
And patent have:
Patent us5109086a discloses a kind of preparation method of vinylidene fluoride copolymers, and the method is using containing 2,3,3,3- tetrafluoros
Propylene monomer modification vinylidene, can improve vinylidene fluoride copolymers compliance, shock resistance, resistance to low temperature, but this side
The polymer reaction yield of method preparation is relatively low.
Patent us3893987a discloses a kind of preparation method of hexafluoro-isobutene/vinylidene copolymerization, and the method can drop
Low polymer fusing point and crystallization temperature, improve Polymer Processing performance, but this preparation method modified monomer consumption is too big.
Patent us6201084b discloses a kind of preparation method of vinylidene thermoplastic copolymer, and the method adopts fluorine-containing
Dioxole and the method for vinylidene copolymerization, improve the impact strength of polymer, but the method have polymer
Complex process, the low problem of polymer yield strength.
Patent us5093427a discloses the preparation method of a kind of vinylidene and hexafluoropropene copolymerization.The method is using breast
Liquid polymerization technique prepares polymer, and emulsion polymerization generally uses perfluoro caprylic acid, and perfluoro caprylic acid is easily adsorbed in product, affects product
Quality, is not easy to degrade, is unfavorable for environmental protection.
Patent us4946900a discloses a kind of preparation method containing vinylidene and CTFE copolymerization.The method is adopted
With stage feeding polymerization, make vinylidene be connected Kynoar with chlorotrifluoroethylene with chemical bond form, improve polymerization
The pliability of thing and impact strength, but stage feeding polymerization technology controlling and process is relative complex, is unfavorable for industrialized production.
Content of the invention
The problems referred to above existing for prior art, it is an object of the invention to design provides a kind of high elongation at tear
The technical scheme of the preparation method of vinylidene fluoride copolymers, the method prepares vinylidene copolymerization using high pressure suspending polymerization technique
Thing, prepared polymer has high elongation at tear, and fusing point is low, and crystallization temperature is low, the features such as impact strength is good, can meet
Electric wire extrudes processing request, has a good application prospect.
A kind of preparation method of the described vinylidene fluoride copolymers of high elongation at tear is it is characterised in that include following walking
Rapid:
1) in airtight polymerization reaction kettle purge nitrogen deoxygenation, add deionized water, initiator, dispersant, chain-transferring agent, second
Monomer, vinylidene fluoride monomers, the consumption of described deionized water is the 300-400% of vinylidene quality, the consumption of described initiator
For the 0.03-0.2% of vinylidene quality, the consumption of described dispersant is the 0.12-0.45% of vinylidene quality, and described chain turns
The consumption moving agent is the 0.1-2.5% of vinylidene quality, and the consumption of described second comonomer is the 1.0- of vinylidene quality
10.0%；
2) temperature of reaction kettle is increased to 30-70 DEG C, reaction pressure is 9.0-12.0mpa, rotating speed is 1000-2000r/min, 4-
Terminate reaction, prepared partial fluorine ethylene polymer slurry after 8 hours；
3) polymer paste high-temperature stirring is deaerated, reclaim unreacted monomer, be washed with deionized slurry to cleaning solution conductance
Rate is down to below 5 μ s/cm, and with filter press collected polymer slurry, the slurry of collection carries out expansion drying finished product.
A kind of preparation method of the described vinylidene fluoride copolymers of high elongation at tear is it is characterised in that in step 1):
The consumption of described deionized water is the 320-380% of vinylidene quality, preferably 330-370%, more preferably 340-360%；Described
The consumption of initiator is the 0.05-0.18% of vinylidene quality, preferably 0.08-0.15%, more preferably 0.1-0.12%；Described
The consumption of dispersant is the 0.15-0.4% of vinylidene quality, preferably 0.2-0.35%, more preferably 0.25-0.3%；Described chain
The consumption of transfer agent is the 0.15-2.2%, preferably 0.18-2.0% of vinylidene quality；The consumption of described second comonomer is inclined
The 2.0-8.0% of PVF quality, preferably 3.0-7.0%, more preferably 4.0-6.0%.
A kind of preparation method of the described vinylidene fluoride copolymers of high elongation at tear is it is characterised in that in step 1):
Described initiator is peroxy dicarbonate dimethyl ester, peroxy dicarbonate diethylester, di-isopropyl peroxydicarbonate, peroxidating
One of two dibutyl carbonates, peroxy dicarbonate di tert butyl carbonate or more than one mixtures；Described dispersant is that perfluor is pungent
Acid, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethylcellulose, poly- second
One of enol or more than one mixtures；Described chain-transferring agent is diethyl carbonate, diethyl malonate, chloroform, second
One of acetoacetic ester, acetone, isopropanol or more than one mixtures；Described second comonomer be 2,3,3,3- tetrafluoropropene,
Trifluoro-ethylene, CTFE, tetrafluoroethene, hexafluoropropene, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid third
Ester, butyl acrylate, methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, third
One of olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate or more than one mixtures.
A kind of preparation method of the described vinylidene fluoride copolymers of high elongation at tear is it is characterised in that step 2) in:
Reaction temperature is 35-65 DEG C, preferably 40-60 DEG C, more preferably 45-50 DEG C；Reaction pressure is 9.5-11.0mpa, preferably 10-
10.5mpa；Rotating speed is 1200-1800r/min, preferably 1300-1700r/min, more preferably 1400-1600r/min；During reaction
Between be 5-7h, preferably 4-6h.
A kind of preparation method of the described vinylidene fluoride copolymers of high elongation at tear is it is characterised in that in step 3):
Polymer paste degassing temperature is 100-121 DEG C, preferably 105-120 DEG C, more preferably 110-115 DEG C；Degassing mixing speed be
500-1000r/min, preferably 600-900r/min, more preferably 700-800r/min；Expansion drying temperature is 100-135 DEG C, excellent
Select 110-130 DEG C, more preferably 120-130 DEG C.
A kind of preparation method of the vinylidene fluoride copolymers of above-mentioned high elongation at tear, using high pressure suspending polymerization technique system
Standby vinylidene fluoride copolymers, prepared polymer has high elongation at tear, and fusing point is low, and crystallization temperature is low, impact strength
Good the features such as, electric wire extrusion processing request can be met, have a good application prospect.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
In following examples and comparative example, method of testing and condition are as follows:
Elongation at break: be measured by gb/t 1040.2-2006, experimental condition: 23 DEG C, 50mm/min.
Fusing point: be measured by astm d3418, experimental condition: nitrogen environment, 10 DEG C/min.
Crystallization temperature: be measured by astm d3418, experimental condition: nitrogen environment, 10 DEG C/min.
Notch impact strength: be measured by astm d6110, experimental condition: 23 DEG C, 4.00mm.
Embodiment 1
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add 300g deionized water, 0.03g initiator ipp, 0.12g dispersion
Agent carboxymethyl sodium cellulosate, 0.1g chain-transferring agent diethyl malonate, 1.0g second comonomer hexafluoropropene, then will react kettle temperature
Degree is increased to 70 DEG C, and is less than 3 DEG C with the fluctuation of cooling water control temperature of reaction kettle, adds vinylidene fluoride monomers with membrane pump and protects
Holding reaction pressure is 9mpa, and rotating speed is 1000r/min, terminates reaction, prepared partial fluorine ethylene polymer slurry after 4 hours.To gather
Compound slurry, at 100 DEG C, is de-gassed under the conditions of mixing speed 500r/min, reclaims unreacted monomer, is washed with deionized
Slurry to cleaning solution electrical conductivity is down to below 5 μ s/cm, and with filter press collected polymer slurry, the slurry of collection is carried out at 100 DEG C
Expansion drying finished product.Test performance, data is shown in Table 1.
Embodiment 2
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add 400g deionized water, 0.2g initiator ipp, 0.45g dispersant
Then temperature of reaction kettle is raised by methylcellulose, 2.5g chain-transferring agent ethyl acetate, 10.0g second comonomer chlorotrifluoroethylene
To 30 DEG C, and it is less than 3 DEG C with the fluctuation of cooling water control temperature of reaction kettle, add vinylidene fluoride monomers with membrane pump and keep reaction
Pressure is 12mpa, and rotating speed is 2000r/min, terminates reaction, prepared partial fluorine ethylene polymer slurry after 8 hours.By polymer syrup
Material, at 121 DEG C, is de-gassed under the conditions of mixing speed 1000r/min, reclaims unreacted monomer, is washed with deionized slurry extremely
Cleaning solution electrical conductivity is down to below 5 μ s/cm, and with filter press collected polymer slurry, the slurry of collection carries out flash distillation at 135 DEG C to be done
Dry finished product.Test performance, data is shown in Table 1.
Embodiment 3
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add 330g deionized water, 0.08g initiator ipp, 0.15g dispersion
Agent hydroxypropyl cellulose, 2.2g chain-transferring agent diethyl malonate, 3.0g second comonomer hydroxyethyl methacrylate, then will be anti-
Answer kettle temperature degree to be increased to 40 DEG C, and be less than 3 DEG C with the fluctuation of cooling water control temperature of reaction kettle, add vinylidene with membrane pump
It is 9.5mpa that monomer keeps reaction pressure, and rotating speed is 1200r/min, terminates reaction, prepared partial fluorine ethylene polymer slurry after 5 hours
Material.By polymer paste at 110 DEG C, it is de-gassed under the conditions of mixing speed 700r/min, reclaim unreacted monomer, use deionization
Water washing slurry to cleaning solution electrical conductivity is down to below 5 μ s/cm, and with filter press collected polymer slurry, the slurry of collection is 110
DEG C carry out expansion drying finished product.Test performance, data is shown in Table 1.
Embodiment 4
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add 350g deionized water, 0.1g initiator ipp, 0.25g dispersant
Then temperature of reaction kettle is raised by hydroxyethyl cellulose, 1.2g chain-transferring agent diethyl malonate, 6.0g second comonomer acrylic acid
To 50 DEG C, and it is less than 3 DEG C with the fluctuation of cooling water control temperature of reaction kettle, add vinylidene fluoride monomers with membrane pump and keep reaction
Pressure is 10mpa, and rotating speed is 1500r/min, terminates reaction, prepared partial fluorine ethylene polymer slurry after 4.5 hours.By polymer
Slurry, at 115 DEG C, is de-gassed under the conditions of mixing speed 800r/min, reclaims unreacted monomer, is washed with deionized slurry
It is down to below 5 μ s/cm to cleaning solution electrical conductivity, with filter press collected polymer slurry, the slurry of collection carries out flash distillation at 120 DEG C
Finished product is dried.Test performance, data is shown in Table 1.
Comparative example 1
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add 380g deionized water, 0.16g initiator ipp, 0.34g dispersion
Then temperature of reaction kettle is increased to 55 DEG C, and uses cooling water by agent hydroxyethyl cellulose, 1.9g chain-transferring agent diethyl malonate
Control temperature of reaction kettle fluctuation to be less than 3 DEG C, add vinylidene fluoride monomers to keep reaction pressure being 9.2mpa with membrane pump, rotating speed
For 1100r/min, after 5.5 hours, terminate reaction, prepared partial fluorine ethylene polymer slurry.By polymer paste at 105 DEG C, stirring
It is de-gassed under the conditions of speed 600r/min, reclaims unreacted monomer, be washed with deionized slurry and drop to cleaning solution electrical conductivity
To below 5 μ s/cm, with filter press collected polymer slurry, the slurry of collection carries out expansion drying finished product at 100 DEG C.Survey
Examination performance, data is shown in Table 1.
Above-described embodiment 1,2,3,4 and comparative example 1 are contrasted, is referred to table 1.
Table 1 shows: the partial fluorine ethylene polymer using the preparation of this method has high elongation at tear, and fusing point is low, crystallization temperature
Low, the features such as notch impact strength is good.The product being obtained using embodiment 1-4, all can reach technique effect of the present invention.
Above technical scheme and embodiment are described in detail to the present invention, but are not limited to the scope of the present invention.
Those skilled in the art for the present invention any obvious conversion or substitute it should also be considered as the protection of the present invention
Scope.
Claims (5)
1. a kind of preparation method of the vinylidene fluoride copolymers of high elongation at tear is it is characterised in that comprise the following steps:
Purge nitrogen deoxygenation in airtight polymerization reaction kettle, add deionized water, initiator, dispersant, chain-transferring agent, the second list
Body, vinylidene fluoride monomers, the consumption of described deionized water is the 300-400% of vinylidene quality, and the consumption of described initiator is
The 0.03-0.2% of vinylidene quality, the consumption of described dispersant is the 0.12-0.45% of vinylidene quality, described chain tra nsfer
The consumption of agent is the 0.1-2.5% of vinylidene quality, and the consumption of described second comonomer is the 1.0-10.0% of vinylidene quality；
Temperature of reaction kettle is increased to 30-70 DEG C, reaction pressure is 9.0-12.0mpa, rotating speed is 1000-2000r/min, 4-8
Terminate reaction, prepared partial fluorine ethylene polymer slurry after hour；
Polymer paste high-temperature stirring is deaerated, reclaims unreacted monomer, be washed with deionized slurry to cleaning solution electrical conductivity
It is down to below 5 μ s/cm, with filter press collected polymer slurry, the slurry of collection carries out expansion drying finished product.
2. as claimed in claim 1 a kind of preparation method of the vinylidene fluoride copolymers of high elongation at tear it is characterised in that
In step 1): the consumption of described deionized water is the 320-380% of vinylidene quality, preferably 330-370%, more preferably 340-
360%；The consumption of described initiator is the 0.05-0.18% of vinylidene quality, preferably 0.08-0.15%, more preferably 0.1-
0.12%；The consumption of described dispersant is the 0.15-0.4% of vinylidene quality, preferably 0.2-0.35%, more preferably 0.25-
0.3%；The consumption of described chain-transferring agent is the 0.15-2.2%, preferably 0.18-2.0% of vinylidene quality；Described second comonomer
Consumption be vinylidene quality 2.0-8.0%, preferably 3.0-7.0%, more preferably 4.0-6.0%.
3. as claimed in claim 1 a kind of preparation method of the vinylidene fluoride copolymers of high elongation at tear it is characterised in that
In step 1): described initiator is peroxy dicarbonate dimethyl ester, peroxy dicarbonate diethylester, peroxy dicarbonate diisopropyl
One of ester, peroxy dicarbonate dibutyl ester, peroxy dicarbonate di tert butyl carbonate or more than one mixtures；Described dispersant
For perfluoro caprylic acid, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium
One of sodium, polyvinyl alcohol or more than one mixtures；Described chain-transferring agent be diethyl carbonate, diethyl malonate,
One of chloroform, ethyl acetate, acetone, isopropanol or more than one mixtures；Described second comonomer is 2,3,3,3- tetra-
Fluoropropene, trifluoro-ethylene, CTFE, tetrafluoroethene, hexafluoropropene, acrylic acid, methyl acrylate, ethyl acrylate, third
Olefin(e) acid propyl ester, butyl acrylate, methyl methacrylate, EMA, propyl methacrylate, methacrylic acid fourth
One of ester, hydroxy-ethyl acrylate, hydroxyethyl methacrylate or more than one mixtures.
4. as claimed in claim 1 a kind of preparation method of the vinylidene fluoride copolymers of high elongation at tear it is characterised in that
Step 2) in: reaction temperature is 35-65 DEG C, preferably 40-60 DEG C, more preferably 45-50 DEG C；Reaction pressure is 9.5-11.0mpa,
It is preferably 10-10.5mpa；Rotating speed is 1200-1800r/min, preferably 1300-1700r/min, more preferably 1400-1600r/
min；Reaction time is 5-7h, preferably 4-6h.
5. as claimed in claim 1 a kind of preparation method of the vinylidene fluoride copolymers of high elongation at tear it is characterised in that
In step 3): polymer paste degassing temperature is 100-121 DEG C, preferably 105-120 DEG C, more preferably 110-115 DEG C；Degassing stirring
Speed is 500-1000r/min, preferably 600-900r/min, more preferably 700-800r/min；Expansion drying temperature is 100-
135 DEG C, preferably 110-130 DEG C, more preferably 120-130 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610722760.2A CN106336476B (en) | 2016-08-25 | 2016-08-25 | preparation method of vinylidene fluoride copolymer with high elongation at break |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610722760.2A CN106336476B (en) | 2016-08-25 | 2016-08-25 | preparation method of vinylidene fluoride copolymer with high elongation at break |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106336476A true CN106336476A (en) | 2017-01-18 |
| CN106336476B CN106336476B (en) | 2019-12-10 |
Family
ID=57825814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610722760.2A Active CN106336476B (en) | 2016-08-25 | 2016-08-25 | preparation method of vinylidene fluoride copolymer with high elongation at break |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106336476B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109065804A (en) * | 2018-07-18 | 2018-12-21 | 湖南烁普新材料有限公司 | A kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application |
| CN110183562A (en) * | 2019-05-30 | 2019-08-30 | 浙江孚诺林化工新材料有限公司 | A kind of partial fluorine ethylene polymer and its preparation method and application for lithium-ion-power cell adhesive |
| CN111518235A (en) * | 2020-06-29 | 2020-08-11 | 天津城建大学 | Water-based vinylidene chloride copolymer resin and preparation method thereof |
| CN113024708A (en) * | 2021-03-15 | 2021-06-25 | 浙江大学衢州研究院 | Method for preparing fluorine-propylene polymer nano material by micro-channel continuous flow |
| WO2022025111A1 (en) * | 2020-07-28 | 2022-02-03 | ダイキン工業株式会社 | Method for preparing fluorine-containing elastomer aqueous dispersion, and fluorine-containing elastomer aqueous dispersion |
| CN114854029A (en) * | 2022-06-01 | 2022-08-05 | 浙江歌瑞新材料有限公司 | Preparation method of polyvinylidene fluoride and cellulose composite material |
| WO2022229361A1 (en) * | 2021-04-29 | 2022-11-03 | Solvay Specialty Polymers Italy S.P.A. | Pvdf fine powders |
| CN116217779A (en) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | High-toughness polyvinylidene fluoride resin and preparation method thereof |
| WO2024082336A1 (en) * | 2022-10-17 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Polymer, conductive slurry, positive electrode plate, secondary battery and electric device |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3893987A (en) * | 1974-05-20 | 1975-07-08 | Allied Chem | Modified hexa fluoroisobutylene/vinylidene fluoride copolymers having improved processing characteristics |
| CN88100574A (en) * | 1987-02-03 | 1988-09-07 | 阿托化学公司 | Heterophasic copolymer of vinylidene and trifluorochloroethylene and preparation method thereof |
| US5095081A (en) * | 1989-03-15 | 1992-03-10 | Solvay & Cie | Process for the manufacture of vinylidene fluoride polymers and use of vinylidene fluoride polymers for paint formulation |
| US5109086A (en) * | 1989-03-15 | 1992-04-28 | Shin-Etsu Chemical Co., Ltd. | Process for producing a vinylidene fluoride copolymer |
| US6187885B1 (en) * | 1990-05-10 | 2001-02-13 | Atofina Chemicals, Inc. | Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same |
| US6201084B1 (en) * | 1996-07-01 | 2001-03-13 | Ausimont S.P.A. | VDF thermoplastic copolymer |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
| CN104725544A (en) * | 2013-12-20 | 2015-06-24 | 浙江蓝天环保高科技股份有限公司 | Novel vinylidene fluoride copolymer with high cohesiveness |
-
2016
- 2016-08-25 CN CN201610722760.2A patent/CN106336476B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3893987A (en) * | 1974-05-20 | 1975-07-08 | Allied Chem | Modified hexa fluoroisobutylene/vinylidene fluoride copolymers having improved processing characteristics |
| CN88100574A (en) * | 1987-02-03 | 1988-09-07 | 阿托化学公司 | Heterophasic copolymer of vinylidene and trifluorochloroethylene and preparation method thereof |
| US5095081A (en) * | 1989-03-15 | 1992-03-10 | Solvay & Cie | Process for the manufacture of vinylidene fluoride polymers and use of vinylidene fluoride polymers for paint formulation |
| US5109086A (en) * | 1989-03-15 | 1992-04-28 | Shin-Etsu Chemical Co., Ltd. | Process for producing a vinylidene fluoride copolymer |
| US6187885B1 (en) * | 1990-05-10 | 2001-02-13 | Atofina Chemicals, Inc. | Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same |
| US6201084B1 (en) * | 1996-07-01 | 2001-03-13 | Ausimont S.P.A. | VDF thermoplastic copolymer |
| CN104725544A (en) * | 2013-12-20 | 2015-06-24 | 浙江蓝天环保高科技股份有限公司 | Novel vinylidene fluoride copolymer with high cohesiveness |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109065804A (en) * | 2018-07-18 | 2018-12-21 | 湖南烁普新材料有限公司 | A kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application |
| CN110183562A (en) * | 2019-05-30 | 2019-08-30 | 浙江孚诺林化工新材料有限公司 | A kind of partial fluorine ethylene polymer and its preparation method and application for lithium-ion-power cell adhesive |
| CN111518235A (en) * | 2020-06-29 | 2020-08-11 | 天津城建大学 | Water-based vinylidene chloride copolymer resin and preparation method thereof |
| WO2022025111A1 (en) * | 2020-07-28 | 2022-02-03 | ダイキン工業株式会社 | Method for preparing fluorine-containing elastomer aqueous dispersion, and fluorine-containing elastomer aqueous dispersion |
| JP7485984B2 (en) | 2020-07-28 | 2024-05-17 | ダイキン工業株式会社 | Method for producing aqueous fluorine-containing elastomer dispersion and aqueous fluorine-containing elastomer dispersion |
| CN113024708A (en) * | 2021-03-15 | 2021-06-25 | 浙江大学衢州研究院 | Method for preparing fluorine-propylene polymer nano material by micro-channel continuous flow |
| WO2022229361A1 (en) * | 2021-04-29 | 2022-11-03 | Solvay Specialty Polymers Italy S.P.A. | Pvdf fine powders |
| CN114854029A (en) * | 2022-06-01 | 2022-08-05 | 浙江歌瑞新材料有限公司 | Preparation method of polyvinylidene fluoride and cellulose composite material |
| WO2024082336A1 (en) * | 2022-10-17 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Polymer, conductive slurry, positive electrode plate, secondary battery and electric device |
| CN116217779A (en) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | High-toughness polyvinylidene fluoride resin and preparation method thereof |
| CN116217779B (en) * | 2023-01-03 | 2024-04-09 | 万华化学集团股份有限公司 | High-toughness polyvinylidene fluoride resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106336476B (en) | 2019-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106336476A (en) | Preparation method of vinylidene fluoride copolymer having high breaking elongation | |
| CN107408699B (en) | Electrode structure and method for manufacturing same | |
| CN105514488B (en) | A kind of binder and its lithium ion battery | |
| EP3118230B1 (en) | Vinylidene fluoride copolymer, method for producing same, gel electrolyte and nonaqueous battery | |
| WO2020238246A1 (en) | Vinylidene fluoride polymer for lithium ion power battery binder, and preparation method therefor and use thereof | |
| CN102336854B (en) | Preparation method for high heat resistance polyvinylidene fluoride | |
| KR102439851B1 (en) | Seperator for secondary battery and secondary battery including the same | |
| KR101168400B1 (en) | Suspension polymerization method for polyvinylchloride and polyvinylchloride produced thereby | |
| CN105518914A (en) | Binder for lithium ion secondary battery electrode, lithium ion secondary battery electrode, production method for lithium ion secondary battery electrode, and lithium ion secondary battery | |
| CN112574498B (en) | Ethylene-vinyl alcohol copolymer resin composition, film and multilayer structure thereof | |
| CN105085762B (en) | A kind of long-chain branch HMW Kynoar and preparation method thereof | |
| CN103304724A (en) | Vinyl chloride-acrylic acid ester-vinyl acetate-acrylic acid copolymerized emulsion | |
| CN102504093B (en) | Method for preparing polyacrylate rubber through continuous solution polymerization and devolatilization extrusion | |
| CN112538130A (en) | Vinylidene fluoride copolymer and preparation method and application thereof | |
| CN106380533B (en) | A kind of polyvinylidene fluoride polymer and preparation method thereof | |
| CN1257921C (en) | Vinylidene polyme and preparing method thereof | |
| CN103524647B (en) | A kind of preparation method of polyvinylidene fluoride resin | |
| WO2011072418A1 (en) | High exchange capacity perfluorinated ion exchange resin, preparation method and use thereof | |
| CN116375915A (en) | Method for preparing ultra-high molecular weight PVDF resin by supercritical polymerization process | |
| CN110317286A (en) | A method of improving polyvinylidene fluoride resin degree of purity | |
| CN104479061A (en) | Vinylidene fluoride modified polyfluorinared ethylene propylene resin and preparation method thereof | |
| CN108192009B (en) | 1, 1-difluoroethylene copolymer and preparation method thereof | |
| KR102208453B1 (en) | Method for preparing polyvinylchloride | |
| CN115322279B (en) | 1, 1-difluoroethylene copolymer and preparation method and application thereof | |
| CN104893189A (en) | Preparation method of enhanced polyvinylidene fluoride resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |